Photochemical Carbonylation and Hydroformylation (funded by BASF)

光化学羰基化和氢甲酰化（巴斯夫资助）

• 批准号: 2754368
• 金额: --
• 依托单位: Imperial College London
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2022
• 资助国家: 英国
• 起止时间: 2022 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2754368
• 关键词: Photochemical; Carbonylation; Hydroformylation; funded; BASF

Synthesizing amides and esters for the production of agrochemical actives, pharmaceutical actives, and other complicated organic molecules is challenging, as high temperatures need to be applied in current state-of-the-art processes. This often results in limited selectivity and consequently in lower yields and margin of the desired product, in some cases the side products of reactions with limited selectivity will have a negative environmental impact and can even prevent registration of agrochemicals. Novel synthetic approaches are therefore desirable that would yield amides and esters at lower temperatures and with better selectivity. For industrial purposes atom-economic and step-economic processes are desirable, as they can save money and improve sustainability by saving energy for separation, and the disposal of side products through better atom economy and step economy. Moreover, they can make green and bio-derived raw-materials amenable. One particularly attractive way of synthesizing amides and esters is by photochemical carbonylation of aryl-halogenides in the presence of amines or alcohols. This reaction will yield the amide or ester via an intermediate carboxylic acid chloride stage at low temperature and possibly therefore with better selectivity. Moreover, this process is extremely attractive in terms of atom economy and step economy. Photochemistry serves at activating the reatents without the need of putting in heat. The reaction follows a different pathway than the transition metal and opens up a new set of paradigms. Photocatalytic utilization of CO will also be attractive for bulk chemicals produced via classical hydroformylation. Rather than using extremely expensive Rh-based catalysts, in the photochemical pathway H2 and CO to form an aldehyde, a novel, photochemical method will be applied that is based on a different mechanism and therefore has the potential of offering opportunities with regard to selectivity over the state-of-the art. The selection of the metal will affect catalysis and offer an opportunity for tuning the chemical product as well as yield and selectivity. This project will require a vivid interest in organic synthetic chemistry and organocatalysis. It will consider the specifics of photo-redox-chemistry in the framework of an interdisciplinary and holistic cluster of six BASF-funded students on photochemistry.

合成酰胺和酯用于生产农用化学活性物质、药物活性物质和其他复杂的有机分子具有挑战性，因为在当前最先进的工艺中需要应用高温。这通常会导致选择性有限，从而导致所需产品的收率和利润较低，在某些情况下，选择性有限的反应副产物会对环境产生负面影响，甚至可能妨碍农用化学品的注册。因此，需要新的合成方法来在较低温度下以更好的选择性生产酰胺和酯。对于工业目的，原子经济和步骤经济过程是可取的，因为它们可以通过节省分离能源来节省资金并提高可持续性，并通过更好的原子经济和步骤经济处理副产物。此外，它们还可以使绿色和生物衍生原材料变得适用。合成酰胺和酯的一种特别有吸引力的方法是在胺或醇存在下通过芳基卤化物的光化学羰基化。该反应将在低温下通过中间体酰氯阶段产生酰胺或酯，因此可能具有更好的选择性。而且，该过程在原子经济性和步骤经济性方面极具吸引力。光化学无需加热即可激活反应物。该反应遵循与过渡金属不同的途径，并开辟了一组新的范例。 CO 的光催化利用对于通过经典加氢甲酰化生产的大宗化学品也很有吸引力。在H2和CO形成醛的光化学途径中，将采用一种基于不同机制的新型光化学方法，而不是使用极其昂贵的Rh基催化剂，因此有可能在选择性方面提供机会最先进的。金属的选择将影响催化作用，并为调整化学产品以及收率和选择性提供机会。该项目需要对有机合成化学和有机催化产生浓厚的兴趣。它将在由六名巴斯夫资助的光化学学生组成的跨学科和整体集群的框架内考虑光氧化还原化学的细节。